CN115073966B - Formamidino salt coating ink and preparation method and application thereof - Google Patents

Formamidino salt coating ink and preparation method and application thereof Download PDF

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CN115073966B
CN115073966B CN202210651603.2A CN202210651603A CN115073966B CN 115073966 B CN115073966 B CN 115073966B CN 202210651603 A CN202210651603 A CN 202210651603A CN 115073966 B CN115073966 B CN 115073966B
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formamidino
perovskite
solvent
film
coating ink
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CN115073966A (en
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徐敬超
邵君
于振瑞
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Wuxi Utmolight Technology Co Ltd
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Wuxi Utmolight Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The application discloses formamidinate coating ink, a preparation method and application thereof, wherein the formamidinate coating ink comprises the following components: the formamidino halide, the inducing additive, the alcohol solvent and the coordination solvent can dissolve the lead halide, so as to obtain the lead halide-coordination solvent-formamidino halide coordination complex intermediate membrane. Therefore, the formamidino salt coating ink can effectively control the nucleation and crystallization process of the perovskite film, induce the highly oriented growth of the perovskite crystal, inhibit the formation of perovskite hetero-phases and improve the phase purity and quality of the perovskite film.

Description

Formamidino salt coating ink and preparation method and application thereof
Technical Field
The application belongs to the field of perovskite solar cells, and particularly relates to formamidino salt coating ink, and a preparation method and application thereof.
Background
It is well known that perovskite solar cells are receiving a great deal of attention by virtue of their exponential increase in efficiency. The tremendous commercial potential has prompted the advent of the perovskite photovoltaic technology industrialization wave. As the core of perovskite solar technology industrialization, perovskite light absorption layer film preparation is particularly critical. The perovskite film layer preparation process by adopting the one-step solution method is relatively simple, and the industrialization is easy to realize. However, the perovskite film layer prepared by the one-step solution method is found to have the problems of difficult control of the crystallization process, short process operation window and the like in the process amplification process.
Disclosure of Invention
The present application aims to solve at least one of the technical problems in the related art to some extent. Therefore, an object of the present application is to provide a formamidinate coating ink, a preparation method and an application thereof, which can effectively control the nucleation and crystallization process of a perovskite film, induce the highly oriented growth of the perovskite crystal, inhibit the formation of a perovskite hetero-phase, and improve the phase purity and quality of the perovskite film.
In one aspect of the application, a formamidino salt coated ink is provided. According to an embodiment of the present application, the formamidino salt coating ink includes a formamidino salt compound having a chemical structural formula of FAX, an inducing additive, an alcohol solvent, and a coordinating solvent, which can dissolve lead halide to obtain a lead halide-coordinating solvent-formamidino salt compound coordination complex intermediate film, wherein X is F - 、Cl - 、Br - 、I - 、SCN - 、BF 4 - 、PF 6 - 、HCOO - Or CH (CH) 3 COO - The induction additive comprises a quaternary mixed additive of methylamine hydrochloride, methylamine hydroiodic acid salt, benzamidine hydrochloride and potassium iodide, wherein the molar ratio of the formamidino salt compound to the induction additive to the coordination solvent is 1 (0.0001-1): 0.05-1.
Therefore, the formamidino salt coating ink can effectively control the nucleation and crystallization process of the perovskite film, induce the highly oriented growth of perovskite crystals, inhibit the formation of perovskite hetero-phases and improve the phase purity and quality of the perovskite film.
In addition, the formamidinate coating ink according to the above embodiment of the present application may have the following additional technical features:
in some embodiments of the application, the inducing additive comprises a substance of the formula MX, wherein M is a primary amine cation, a secondary amine cation, a tertiary amine cation, an ethylamino-cation, a benzamidine cation, a guanidine cation, cs + 、Rb + 、K + X is F - 、Cl - 、Br - 、I - 、SCN - 、BF 4 - 、PF 6 - 、HCOO - Or CH (CH) 3 COO - . Thereby effectively controlling the nucleation and crystallization process of the perovskite film, inducing the highly oriented growth of the perovskite crystal, simultaneously inhibiting the formation of perovskite hetero-phase,improving the phase purity of the perovskite film.
In some embodiments of the application, the alcohol solvent comprises at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, and tert-butanol.
In some embodiments of the application, the coordinating solvent comprises at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylformamide, dimethylsulfoxide, N-methylpyrrolidone, and 1, 3-dimethyl-2-imidazolidinone.
In some embodiments of the present application, the formamidinate coating ink has a concentration of 0.1 to 2mol/L.
In some embodiments of the application, the formamidinate-coated ink is suitable for use in applications including at least one of slot coating, bar blade coating, inkjet printing, and spray coating.
In a second aspect of the present application, the present application provides a method of preparing the formamidino salt coated ink described above. According to an embodiment of the application, the method comprises:
(1) Dissolving formamidino salt compound in an alcohol solvent to obtain a first precursor liquid;
(2) Dissolving an induction additive in a coordinating solvent so as to obtain a second precursor liquid;
(3) And mixing the first precursor liquid and the second precursor liquid so as to obtain formamidino-salt coating ink.
Therefore, the formamidino salt coating ink which can effectively control the nucleation and crystallization process of the perovskite film, induce the highly oriented growth of the perovskite crystal, inhibit the formation of perovskite hetero-phase and improve the phase purity and quality of the perovskite film can be prepared by adopting the method of the application. In addition, the formamidino salt coating ink has good universality and can be suitable for relevant coating or printing processes such as slit coating, bar blade coating, ink-jet printing, spraying and the like.
In a third aspect of the application, the application provides a method of preparing a perovskite film. According to an embodiment of the application, the method comprises: the formamidino salt coating ink or the formamidino salt coating ink obtained by the method is applied on a lead halide film, the coordination solvent dissolves the lead halide, and then the lead halide-coordination solvent-formamidino salt compound coordination complex intermediate film is obtained, and then annealing is carried out, so that the perovskite film is obtained. Therefore, the method realizes the controllable nucleation and crystallization process of the perovskite film layer, improves the stability and repeatability of the process for preparing the perovskite film, simplifies the preparation process of the perovskite film and reduces the process cost.
In a fourth aspect of the application, the application provides a perovskite film. According to an embodiment of the application, the perovskite film is prepared by the method. Therefore, the nucleation crystallization process of the perovskite film can be effectively controlled, the highly oriented growth of the perovskite crystal is induced, and the formation of perovskite hetero-phases is inhibited, so that the phase purity and quality of the perovskite film are improved.
In a fifth aspect of the application, the application proposes a perovskite solar cell. According to an embodiment of the present application, the perovskite solar cell includes: the transparent conductive layer, the first charge transmission layer, the perovskite layer, the second charge transmission layer and the electrode layer, wherein the perovskite layer is a perovskite film obtained by adopting the method or the perovskite film. Thus, the photoelectric performance of the perovskite solar cell is improved.
In a sixth aspect of the application, the application provides a method of making a perovskite solar cell as described above. According to an embodiment of the application, the method comprises: (a) Depositing a first charge transport layer on the transparent conductive layer; (b) Depositing a lead halide film on the first charge transport layer, then applying the above formamidino salt coating ink or the formamidino salt coating ink obtained by the above method on the lead halide film, dissolving the lead halide by the coordination solvent, further obtaining a lead halide-coordination solvent-formamidino salt compound coordination complex intermediate film, and then annealing to form a perovskite film on the first charge transport layer; (c) And sequentially forming a second charge transport layer and an electrode layer on the perovskite film so as to obtain the perovskite solar cell. Thus, the perovskite solar cell with excellent photoelectric properties can be prepared by the method.
Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application.
Drawings
The foregoing and/or additional aspects and advantages of the application will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic flow diagram of a method of preparing formamidinate-coated ink according to one embodiment of the application;
FIG. 2 is a schematic structural view of a perovskite solar cell according to one embodiment of the application;
FIG. 3 is a schematic flow diagram of a method of fabricating a perovskite solar cell according to one embodiment of the application;
FIG. 4 is an XRD pattern of the formamidino perovskite films obtained by the preparation of examples 1 to 3 and comparative examples 1 to 2;
FIG. 5 is an SEM image of a formamidino perovskite film obtained according to example 1;
FIG. 6 is an SEM image of a formamidino perovskite film obtained according to example 2;
FIG. 7 is an SEM image of a formamidino perovskite film obtained according to example 3;
FIG. 8 is an SEM image of a formamidino perovskite film obtained according to comparative example 1;
FIG. 9 is an SEM image of a formamidino perovskite film obtained by comparative example 2.
Description of the drawings:
100. a transparent conductive layer;
200. a first charge transport layer;
300. a perovskite film;
400. a second charge transport layer;
500. an electrode layer.
Detailed Description
The embodiments described below by referring to the drawings are illustrative and intended to explain the present application and should not be construed as limiting the application.
In a first aspect of the application, the application provides a formamidino salt coated ink. According to an embodiment of the present application, the formamidino salt coating ink includes a formamidino salt compound having a chemical structural formula of FAX, wherein X is F, an inducing additive, an alcohol solvent, and a coordinating solvent that can dissolve a lead halide to thereby obtain a lead halide-coordinating solvent-formamidino salt compound coordination complex intermediate film - 、Cl - 、Br - 、I - 、SCN - 、BF 4 - 、PF 6 - 、HCOO - Or CH (CH) 3 COO - The induction additive comprises a quaternary mixed additive of methylamine hydrochloride, methylamine hydroiodic acid salt, benzamidine hydrochloride and potassium iodide, wherein the molar ratio of the formamidino salt compound to the induction additive to the coordination solvent is 1 (0.0001-1): 0.05-1.
The inventor finds that the lead halide can be dissolved by compounding the formamidino salt compound, the inducing additive, the alcohol solvent and the coordination solvent into formamidino salt coating ink, so that the lead halide and the formamidino salt compound can be subjected to full chemical reaction, an intermediate state film of the coordination complexing of the lead halide-coordination solvent-formamidino salt compound is obtained, various requirements on the morphological characteristics, the crystalline structure, the porosity and the like of the lead halide film are reduced, and the high-quality perovskite film is more favorable to be formed. The induction additive can effectively control the nucleation and crystallization process of the perovskite film, induce the highly oriented growth of perovskite crystals, inhibit the formation of perovskite hetero-phases and improve the phase purity of the perovskite film. The addition of the alcohol solvent is beneficial to green, economical, environment-friendly and safe production of the perovskite film. In addition, the formamidino salt coating ink has good universality and can be suitable for relevant coating or printing processes such as slit coating, bar blade coating, ink-jet printing, spraying and the like. Therefore, the formamidino salt coating ink can effectively control the nucleation and crystallization process of the perovskite film, induce the highly oriented growth of perovskite crystals, inhibit the formation of perovskite hetero-phases and improve the phase purity and quality of the perovskite film.
The formamidino salt compound has a chemical structural formula of FAX, wherein X is F - 、Cl - 、Br - 、I - 、SCN - 、BF 4 - 、PF 6 - 、HCOO - Or CH (CH) 3 COO - Preferably, amitraz hydroiodinate FAI; the inducing additive comprises a substance with a chemical structural formula of MX, wherein M is primary amine cation, secondary amine cation, tertiary amine cation, ethylamidine cation, benzamidine cation, guanidine cation, cs + 、Rb + 、K + X is F - 、Cl - 、Br - 、I - 、SCN - 、BF 4 - 、PF 6 - 、HCOO - Or CH (CH) 3 COO - Preferably, the quaternary mixed additive of methylamine hydrochloride MACl, methylamine hydroiodinated MAI, benzamidine hydrochloride PhFACl and potassium iodide KI. Therefore, the induction additive with the composition can effectively control the nucleation and crystallization process of the perovskite film, induce the highly oriented growth of the perovskite crystal, inhibit the formation of perovskite hetero-phases and improve the phase purity of the perovskite film.
Further, the specific types of the alcohol solvent and the coordinating solvent may be selected by those skilled in the art according to actual needs, so long as the above functions can be achieved, for example, the above alcohol solvents include, but are not limited to, at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol and tert-butanol, preferably a binary mixed solvent of isopropanol and n-butanol; the above-mentioned complexing solvents include, but are not limited to, at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylformamide, dimethylsulfoxide, N-methylpyrrolidone and 1, 3-dimethyl-2-imidazolidinone, preferably a binary mixed complexing solvent of dimethylsulfoxide DMSO and N-methylformamide NMF.
Further, the molar ratio of the formamidino salt compound, the inducing additive and the coordination solvent is 1 (0.0001-1): 0.05-1. The inventors found that if the addition amount of the inducing additive is excessive, the formation of a large amount of heterogeneous perovskite is caused, thereby reducing the phase purity of the formamidino perovskite film; if the addition amount of the inducing additive is too small, perovskite crystals cannot be grown in a highly oriented manner, and the crystal size is small and defects are large. If the addition amount of the coordination solvent is too large, a large amount of dendrites are generated, and a continuous and compact black-phase formamidino perovskite film cannot be obtained; if the addition amount of the coordinating solvent is too small, a stable coordination complex intermediate film of the lead halide-coordinating solvent-formamidino salt compound cannot be formed, which is unfavorable for the efficient conversion of lead halide into formamidino perovskite film. Further, the concentration of the formamidino salt coating ink is 0.1-2 mol/L;
in a second aspect of the application, the application provides a method of preparing a formamidino salt coated ink. Referring to fig. 1, according to an embodiment of the present application, the method includes:
s100: dissolving formamidino salt compound in alcohol solvent
In this step, a formamidino salt compound is dissolved in an alcohol solvent to obtain a first precursor liquid. The addition of the alcohol solvent ensures the green, economical, environment-friendly and safe preparation of the subsequent perovskite film. It should be noted that the specific types of the formamidinium salt compound and the alcohol solvent are the same as those described above, and will not be repeated here.
S200: dissolving the inducing additive in a coordinating solvent
In this step, the inducing additive is dissolved in the coordinating solvent to obtain the second precursor solution. The induction additive can effectively control the nucleation and crystallization process of the perovskite film, induce the highly oriented growth of perovskite crystals, inhibit the formation of perovskite hetero-phases and improve the phase purity of the perovskite film. The coordination solvent can dissolve the lead halide and enable the lead halide to fully perform chemical reaction with formamidino salt compound, thereby reducing various requirements on the morphology feature, crystalline structure, porosity and the like of the lead halide film and being more beneficial to forming a high-quality perovskite film.
It should be noted that, the specific types of the inducing additive and the coordinating solvent are the same as those described above, and the mixing ratio of the formamidinium salt compound, the inducing additive and the coordinating solvent is also the same as that described above, and will not be described here again.
S300: mixing the first precursor liquid and the second precursor liquid
In this step, the first precursor liquid and the second precursor liquid are mixed to obtain formamidino salt coating ink. Specifically, the concentration of the formamidinate coating ink is 0.1-2 mol/L.
Therefore, the formamidino salt coating ink prepared by the method can effectively control the nucleation and crystallization process of the perovskite film, induce the highly oriented growth of the perovskite crystal, inhibit the formation of perovskite hetero-phases and improve the phase purity and quality of the perovskite film. It should be noted that the features and advantages described above for the formamidinate-coated ink are equally applicable to the method for preparing the formamidinate-coated ink, and are not described here again.
In a third aspect of the application, the application provides a method of preparing a perovskite film. According to an embodiment of the application, the method comprises: the formamidino salt coating ink or the formamidino salt coating ink obtained by the method is applied on a lead halide film, a coordination solvent dissolves lead halide, and then a lead halide-coordination solvent-formamidino salt compound coordination complex intermediate film is obtained, and then annealing is carried out, so that a perovskite film is obtained.
Therefore, the method realizes the controllable nucleation and crystallization process of the perovskite film layer, improves the stability and repeatability of the process for preparing the perovskite film, simplifies the preparation process of the perovskite film and reduces the process cost. It should be noted that the features and advantages described above for the formamidinate coating ink and the preparation method thereof are also applicable to the method for preparing the perovskite film, and are not described herein.
In a fourth aspect of the application, the application provides a perovskite film. According to an embodiment of the application, the perovskite film is prepared by the method.
Therefore, the nucleation crystallization process of the perovskite film can be effectively controlled, the highly oriented growth of the perovskite crystal is induced, and the formation of perovskite hetero-phases is inhibited, so that the phase purity and quality of the perovskite film are improved. It should be noted that the features and advantages described above for the formamidinate coating ink, the preparation method thereof, and the method for preparing the perovskite film are also applicable to the perovskite film, and are not described herein.
In a fifth aspect of the application, the application proposes a perovskite solar cell. According to an embodiment of the present application, referring to fig. 2, the perovskite solar cell includes a transparent conductive layer 100, a first charge transport layer 200, a perovskite layer 300, a second charge transport layer 400, and an electrode layer 500, wherein the perovskite layer 300 is a perovskite film obtained by the above-described method or the above-described perovskite film. It should be noted that the transparent conductive layer 100, the first charge transport layer 200, the second charge transport layer 400, and the electrode layer 500 are all made of conventional materials, and are not described herein again.
Thus, by adopting a perovskite film having high phase purity and quality as a perovskite layer in a perovskite solar cell, the photoelectric properties of the perovskite solar cell are improved. It should be noted that the features and advantages described above for the formamidinate coating ink, the method for preparing the perovskite film, and the perovskite film are also applicable to the perovskite solar cell, and are not described herein.
In a sixth aspect of the application, the application provides a method of making the perovskite solar cell described above. Referring to fig. 3, according to an embodiment of the present application, the method includes:
sa: depositing a first charge transport layer on the transparent conductive layer
In this step, a first charge transport layer is deposited on the transparent conductive layer. The specific manner of deposition is not particularly limited, and deposition may be performed using, for example, a magnetron sputtering method.
Sb: depositing a lead halide film on the first charge transport layer, then applying a formamidinium salt coating ink to the lead halide film, and then annealing
In this step, a lead halide film is deposited on the first charge transport layer, then formamidino salt coating ink is applied on the lead halide film, a coordination solvent can dissolve the lead halide, further a lead halide-coordination solvent-formamidino salt compound coordination complex intermediate film is obtained, then annealing is performed, and finally a perovskite film is formed on the first charge transport layer. The method of applying the formamidinium salt coating ink to the lead halide film is not particularly limited, and for example, a relevant coating or printing process such as slit coating, bar blade coating, ink jet printing, spray coating, or the like may be used.
Sc: sequentially forming a second charge transport layer and an electrode layer on the perovskite film
In the step, a second charge transport layer and an electrode layer are sequentially formed on the perovskite film, and the perovskite solar cell is obtained.
Thus, the perovskite solar cell with excellent photoelectric properties can be prepared by the method. The manner of sequentially forming the second charge transport layer and the electrode layer on the perovskite film is not particularly limited, and includes, for example, at least one of reactive plasma deposition and magnetron sputtering.
It should be noted that the features and advantages described above for the perovskite film and the preparation method thereof are also applicable to the method for preparing the perovskite solar cell, and are not described herein.
The following detailed description of embodiments of the application is provided for the purpose of illustration only and is not to be construed as limiting the application. In addition, all reagents employed in the examples below are commercially available or may be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
The method for preparing formamidino salt coating ink comprises the following steps:
(1) FAI is dissolved in a mixed solvent of isopropyl alcohol and n-butyl alcohol (the volume ratio of isopropyl alcohol to n-butyl alcohol is 4:1) to obtain a first precursor solution with the concentration of 0.5 mol/L;
(2) Dissolving 0.2 mol of MACl, 0.15 mol of MAI, 0.001 mol of PhFACl and 0.01 mol of KI in 0.15 mol of DMSO and NMF mixed coordination solvent (the volume ratio of DMSO to NMF is 95:5) to obtain a second precursor solution;
(3) And mixing the first precursor liquid and the second precursor liquid according to the volume ratio of 1:1 to obtain the formamidino salt coating ink.
The method for preparing the perovskite battery comprises the following steps:
(a) Cleaning FTO conductive glass, and performing magnetron sputtering deposition on a nickel oxide film with the thickness of 25 nm on the surface of the clean FTO glass, wherein no post-treatment is needed, and taking out the glass for later use after the deposition is finished;
(b) The PbI with the thickness of 300 nm is deposited on the surface of the nickel oxide film obtained in the step (1) through direct current sputtering 2 The film is taken out for standby after deposition is completed without any post treatment;
(c) Filtering the formamidino salt coating ink obtained in the above step and then slot-coating the PbI obtained in the step (b) 2 The film surface is coated to obtain FAI-DMSO-PbI 2 -NMF coordination complex intermediate, and finally annealing the coordination complex intermediate for 20 minutes at 150 ℃ to obtain formamidino perovskite film, and cooling for standby;
(d) Depositing the niobium oxide film of 30 nm on the surface of the perovskite film obtained in the step (c) by using reactive plasma, and taking out the perovskite film for standby after the deposition is completed without any post-treatment;
(e) And (d) performing magnetron sputtering on the surface of the niobium oxide film obtained in the step (d) to obtain aluminum-doped zinc oxide with the thickness of 150 nm, thereby obtaining the perovskite solar cell.
Example 2
The method for preparing formamidino salt coating ink comprises the following steps:
(1) FAI is dissolved in a mixed solvent of isopropyl alcohol and n-butyl alcohol (the volume ratio of isopropyl alcohol to n-butyl alcohol is 4:1) to obtain a first precursor solution with the concentration of 0.5 mol/L;
(2) Dissolving 0.05 mol of MACl, 0.05 mol of MAI, 0.001 mol of PhFACl and 0.01 mol of KI in 0.15 mol of DMSO and NMF mixed coordination solvent (the volume ratio of DMSO to NMF is 95:5) to obtain a second precursor solution;
(3) And mixing the first precursor liquid and the second precursor liquid according to the volume ratio of 1:1 to obtain the formamidino salt coating ink.
The method for preparing the perovskite battery comprises the following steps:
removing step (c) "the formamidinate-coated ink obtained above is filtered and then the bar is blade-coated on the PbI obtained in step (b) 2 The film surface is coated to obtain FAI-DMSO-PbI 2 -NMF coordination complex intermediate, and finally annealing the coordination complex intermediate at 150 ℃ for 20 minutes to obtain formamidino perovskite film, wherein the steps (a), (b), (d) and (e) are the same as those of example 1 except that the process is different from example 1 and cooling for standby.
Example 3
The method for preparing formamidino salt coating ink comprises the following steps:
(1) FAI is dissolved in a mixed solvent of isopropyl alcohol and n-butyl alcohol (the volume ratio of isopropyl alcohol to n-butyl alcohol is 4:1) to obtain a first precursor solution with the concentration of 0.5 mol/L;
(2) Dissolving 0.2 mol of MACl, 0.15 mol of MAI, 0.001 mol of PhFACl and 0.01 mol of KI in 0.5 mol of DMSO and NMF mixed coordination solvent (the volume ratio of DMSO to NMF is 95:5) to obtain a second precursor solution;
(3) And mixing the first precursor liquid and the second precursor liquid according to the volume ratio of 1:1 to obtain the formamidino salt coating ink.
The method for producing the perovskite battery was the same as in example 1.
Comparative example 1
The method for preparing formamidino salt coating ink comprises the following steps:
(1) FAI is dissolved in a mixed solvent of isopropyl alcohol and n-butyl alcohol (the volume ratio of isopropyl alcohol to n-butyl alcohol is 4:1) to obtain a first precursor solution with the concentration of 0.5 mol/L;
(2) A mixture-inducing additive of 0.2 mol MACl, 0.15 mol MAI, 0.001 mol PhFACl and 0.01 mol KI was dissolved in the first precursor solution, and mixed to obtain a formamidino-salt coating ink.
The procedure of the method for producing the perovskite battery was the same as in example 1.
Comparative example 2
The method for preparing formamidino salt coating ink comprises the following steps:
(1) FAI is dissolved in a mixed solvent of isopropyl alcohol and n-butyl alcohol (the volume ratio of isopropyl alcohol to n-butyl alcohol is 4:1) to obtain a first precursor solution with the concentration of 0.5 mol/L;
(2) 0.15 mol of a mixed coordination solvent of DMSO and NMF is added into the first precursor solution, and the mixed coordination solvent is mixed to obtain formamidino salt coating ink.
The procedure of the method for producing the perovskite battery was the same as in example 1.
XRD patterns of the formamidino perovskite films prepared in examples 1 to 3 and comparative examples 1 to 2 were characterized, and the results are shown in FIG. 4. As can be seen from fig. 4, the formamidino perovskite film prepared in example 1 has significant perovskite crystal orientation and high crystal quality; the formamidino perovskite films prepared in example 2 and example 3 are compared with comparative example 1 and comparative example 2, pbI 2 The residual quantity of the crystal is less, the crystal orientation is higher, and the crystal quality is better; comparative example 1 shows that the formamidino perovskite film prepared by the method has a large amount of PbI 2 Residual, indicating a large amount of PbI 2 Failure to convert efficiently to formamidino perovskite membranes; the formamidino perovskite film prepared in the comparative example 2 has poor crystal orientation, which indicates that a large amount of perovskite crystals grow out of order.
SEM test was conducted on the formamidino perovskite films prepared in examples 1 to 3 and comparative examples 1 to 2. As can be seen from fig. 5, the formamidino perovskite film prepared in example 1 has an oversized crystal grain size, and the crystal grains are densely packed and have a smooth surface; as can be seen from fig. 6, the formamidino perovskite film prepared in example 2 has a larger grain size, and the crystals are densely packed and have good crystallinity compared with comparative examples 1 and 2; as can be seen from fig. 7, the formamidino perovskite film prepared in example 3 has an ultra-large grain size, and the crystal packing is more compact and the crystal crystallinity is good compared with comparative examples 1 and 2; as can be seen from FIG. 8, the formamidino perovskite film obtained in comparative example 1 had a large amount of PbI 2 Residual perovskite crystal grain size is small, and a large number of crystal boundaries exist; as can be seen from FIG. 9, the formamidino perovskite prepared in comparative example 2A large number of holes appear on the surface of the film, and the crystal grains are not stacked continuously, so that the crystallization quality is poor.
The perovskite solar cells obtained in examples 1 to 3 and comparative examples 1 to 2 were subjected to performance test, and the results are shown in Table 1:
TABLE 1 perovskite solar cell performance parameters prepared by examples 1-3 and comparative examples 1-2
As can be seen from the data in Table 1, the perovskite solar cells prepared in examples 1-3 have excellent photoelectric properties, while the perovskite solar cells prepared in comparative examples 1-2 have relatively poor photoelectric properties, which indicates that the formamidino-salt-coated ink prepared in the application can realize a large-area homogeneous perovskite thin film, thereby paving a road for commercialization of perovskite photovoltaic technology.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present application have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the application, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the application.

Claims (12)

1. A formamidino-salt coating ink is characterized by comprising a formamidino-salt compound, an inducing additive, an alcohol solvent and a coordination solvent, wherein the coordination solvent can dissolve lead halide, so as to obtain a lead halide-coordination solvent-formamidino-salt compound coordination complex intermediate membrane, and the formamidino-salt compound has a chemical structural formula of FAX, wherein X is F - 、Cl - 、Br - 、I - 、SCN - 、BF 4 - 、PF 6 - 、HCOO - Or CH (CH) 3 COO - The induction additive comprises a quaternary mixed additive of methylamine hydrochloride, methylamine hydroiodic acid salt, benzamidine hydrochloride and potassium iodide, wherein the molar ratio of the formamidino salt compound to the induction additive to the coordination solvent is 1 (0.0001-1): 0.05-1.
2. The formamidinate-coated ink of claim 1, wherein the alcohol solvent comprises at least one of methanol, ethanol, propanol, and butanol.
3. The formamidinate-coated ink of claim 1, wherein the alcohol solvent comprises a binary mixed solvent of isopropyl alcohol and n-butanol.
4. The formamidinate-coated ink of claim 1, wherein the coordinating solvent comprises at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylformamide, dimethylsulfoxide, N-methylpyrrolidone, and 1, 3-dimethyl-2-imidazolidinone.
5. The formamidinate coating ink of claim 1, wherein the coordinating solvent comprises a binary mixed solvent of dimethyl sulfoxide and N-methyl formamide.
6. The formamidinate coating ink of any one of claims 1-5, wherein the formamidinate coating ink has a concentration of 0.1-2 mol/L.
7. The formamidinate coating ink of any one of claims 1-5, wherein the formamidinate coating ink is suitable for use in at least one of slot coating, bar blade coating, inkjet printing, and spray coating.
8. A method of preparing the formamidino salt coating ink of any one of claims 1-7, comprising:
(1) Dissolving formamidino salt compound in an alcohol solvent to obtain a first precursor liquid;
(2) Dissolving an induction additive in a coordinating solvent so as to obtain a second precursor liquid;
(3) And mixing the first precursor liquid and the second precursor liquid so as to obtain formamidino-salt coating ink.
9. A method for producing a perovskite film, characterized in that the formamidino-salt coating ink according to any one of claims 1 to 7 or the formamidino-salt coating ink obtained by the method according to claim 8 is applied on a lead halide film, the coordination solvent dissolves lead halide, and thus a lead halide-coordination solvent-formamidino-salt compound coordination complex intermediate film is obtained, followed by annealing, to obtain a perovskite film.
10. A perovskite film prepared by the method of claim 9.
11. A perovskite solar cell, comprising: a transparent conductive layer, a first charge transport layer, a perovskite layer, a second charge transport layer, and an electrode layer, wherein the perovskite layer is a perovskite film obtained by the method of claim 9 or a perovskite film of claim 10.
12. A method of making the perovskite solar cell of claim 11, comprising:
(a) Depositing a first charge transport layer on the transparent conductive layer;
(b) Depositing a lead halide thin film on the first charge transport layer, then applying the formamidino salt coating ink according to any one of claims 1 to 7 or the formamidino salt coating ink obtained by the method according to claim 8 on the lead halide thin film, the coordinating solvent dissolving the lead halide, thereby obtaining a lead halide-coordinating solvent-formamidino salt compound coordination complex intermediate film, and then annealing to form a perovskite film on the first charge transport layer;
(c) And sequentially forming a second charge transport layer and an electrode layer on the perovskite film so as to obtain the perovskite solar cell.
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